study of the effect of amino-functionalized multiwall

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ORIGINAL PAPER Study of the effect of amino-functionalized multiwall carbon nanotubes on dry sliding wear resistance properties of carbon fiber reinforced thermoset polymers G. Pincheira 1 C. Montalba 1 W. Gacitua 3 H.-M. Montrieux 4 J. Lecomte-Beckers 4 M. F. Mele ´ndrez 1 P. Flores 1,2 Received: 30 July 2015 / Revised: 26 November 2015 / Accepted: 5 January 2016 Ó Springer-Verlag Berlin Heidelberg 2016 Abstract This work investigates the effect of multiwall carbon nanotubes (MWCNTs) on the mechanical and tribological behavior of a fiber reinforced composite (FRC). Fiber reinforced composites and nano-engineered FRCs are manufactured by resin transfer molding. In-plane tensile tests, in-plane shear tests and through-thickness compression tests are used to assess the influence of MWCNTs on the material mechanical behavior. Pin on disk dry sliding tests are used to quantify the effect of MWCNTs on the friction coefficient and the specific wear rate. It was determined that (1) MWCNTs have an influence on the improvement on both the through-thickness compression strength and the specific wear rate, and (2) they do not influence the material stiffness, in-plane tensile and shear strengths and the friction coefficient. It is assumed that the observed improvements are due to the demonstrated positive influence of the MWCNTs effect on the matrix/reinforcement interfacial strength and on the matrix fracture toughness. Keywords Multiwall carbon nanotubes Fiber reinforced composites Mechanical testing Wear resistance & P. Flores pfl[email protected] 1 Department of Materials Engineering (DIMAT), Faculty of Engineering, University of Concepcion, 270 Edmundo Larenas, Box 160-C, 4070409 Concepcion, Chile 2 Department of Mechanical Engineering (DIM), Faculty of Engineering, University of Concepcion, 219 Edmundo Larenas, Box 160-C, 4070409 Concepcion, Chile 3 Department of Wood Engineering, University of Bı ´o-Bı ´o, Collao 1202, Box 5-C, 4081112 Concepcion, Chile 4 Special Metallic Materials, B52, University of Liege, 1 Chemin des Chevreuils, Sart Tilman, 4000 Liege, Belgium 123 Polym. Bull. DOI 10.1007/s00289-016-1608-4

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ORIGINAL PAPER

Study of the effect of amino-functionalized multiwallcarbon nanotubes on dry sliding wear resistanceproperties of carbon fiber reinforced thermosetpolymers

G. Pincheira1 • C. Montalba1 • W. Gacitua3 • H.-M. Montrieux4 •

J. Lecomte-Beckers4 • M. F. Melendrez1 • P. Flores1,2

Received: 30 July 2015 / Revised: 26 November 2015 / Accepted: 5 January 2016

� Springer-Verlag Berlin Heidelberg 2016

Abstract This work investigates the effect of multiwall carbon nanotubes

(MWCNTs) on the mechanical and tribological behavior of a fiber reinforced

composite (FRC). Fiber reinforced composites and nano-engineered FRCs are

manufactured by resin transfer molding. In-plane tensile tests, in-plane shear tests

and through-thickness compression tests are used to assess the influence of

MWCNTs on the material mechanical behavior. Pin on disk dry sliding tests are

used to quantify the effect of MWCNTs on the friction coefficient and the specific

wear rate. It was determined that (1) MWCNTs have an influence on the

improvement on both the through-thickness compression strength and the specific

wear rate, and (2) they do not influence the material stiffness, in-plane tensile and

shear strengths and the friction coefficient. It is assumed that the observed

improvements are due to the demonstrated positive influence of the MWCNTs

effect on the matrix/reinforcement interfacial strength and on the matrix fracture

toughness.

Keywords Multiwall carbon nanotubes � Fiber reinforced composites �Mechanical testing � Wear resistance

& P. Flores

[email protected]

1 Department of Materials Engineering (DIMAT), Faculty of Engineering, University of

Concepcion, 270 Edmundo Larenas, Box 160-C, 4070409 Concepcion, Chile

2 Department of Mechanical Engineering (DIM), Faculty of Engineering, University of

Concepcion, 219 Edmundo Larenas, Box 160-C, 4070409 Concepcion, Chile

3 Department of Wood Engineering, University of Bıo-Bıo, Collao 1202, Box 5-C,

4081112 Concepcion, Chile

4 Special Metallic Materials, B52, University of Liege, 1 Chemin des Chevreuils, Sart Tilman,

4000 Liege, Belgium

123

Polym. Bull.

DOI 10.1007/s00289-016-1608-4

Introduction

The study of the tribological behavior of fiber reinforced composites (FRCs) based

on polymer matrix increases the possibilities for machine elements optimal design.

The constituents (type and content) of the FRCs play a relevant role on the material

mechanical behavior, wear rate and friction coefficient. Hence, a proper material

design must be focused on the required application. FRCs have been demonstrated

to be self-lubricant [1, 2] and corrosion resistant besides having the proper

mechanical performance (specific stiffness and strength, fracture toughness, fatigue

behavior) for structural applications. This multifunctional feature of FRCs is

interesting for machine element design, as shown in [3–6], during the designing of

bearings.

To improve the composite wear behavior, some research has been focused on the

study of the influence of fillers in the matrix on the material wear resistance. Larsen

et al. [7] reported that the addition of nano-CuO (1 vol.%) and micro-scale PTFE

(5 vol.%) particles (separately) on the reinforcement of epoxy carbon/aramid fibers

has a minor improvement in wear, but without producing differences in friction.

These authors concluded that the friction and wear properties are controlled by the

fibers. Su et al. [8] reported that the addition of nano-CaCO3 (5 wt.%), nano-SiO2

(5 wt.%) and nano-TiO2 (5 wt.%) contributed to increase the wear resistance a

carbon fabric/phenolic resin composite. This improvement is associated with the

observed changes on the transfer film. Suresha et al. [9] reduced wear in epoxy

carbon fiber reinforced by using a graphite filler (5 and 10 wt.%). The wear

reduction using graphite filler is associated with reduction in the removal of fiber, a

phenomenon that can be linked to the switch of the wear mechanism from

microcracking to microplowing/microcutting. The above examples were developed

under dry sliding conditions.

The improvement of the bonding at the matrix/reinforcement interface can

reduce the removal of fiber. Indeed, as established by Lee et al. [10], if the fracture

toughness of the matrix/reinforcement interface exceeds the minimum toughness of

either constituent and the fracture in the reinforcement is not favorable, the resulting

wear debris will be smaller in relation to the reinforcement size, thereby improving

the wear resistance.

Several authors, using different manufacturing techniques, have demonstrated

that the incorporation of multiwall carbon nanotubes (MWCNTs) on FRCs increases

the strength of the matrix/reinforcement interface. For example, in [11–13]

MWCNTs were grafted onto carbon fibers using the chemical vapor deposition

method, whereas [14] and [15] described the modification of the surface of sized

fibers by aqueous suspension deposition of MWCNTs. In addition, [15] and [16]

described the dispersion of MWCNTs into the resin (epoxy) to prepare a suspension.

For each of the reported techniques, significant improvements on the epoxy/fiber/

MWCNTs interfacial shear strength (IFSS) were obtained (from 11 % [12] to

175 % [11]), with the amount of improvement depending on the chosen technique,

the orientation and length of the MWCNTs, as well as the content (as established by

the model proposed by Yang et al. [17]) and the surface treatment of the MWCNTs,

Polym. Bull.

123

among other features. According to [18], the increase of the IFSS due to the addition

of MWCNTs can explain the increase of the interlaminar shear strength (ILSS). The

addition of MWCNTs to the resin or to the FRCs also increases the material fracture

toughness of the material, as demonstrated in [19] or [20] for epoxy resin and in

[21–24] for FRCs (glass fiber and carbon fiber reinforcement).

Besides, experimental evidence has established that the addition of MWCNTs in

epoxy resin enhances its wear resistance. Friederich and Schlarb [25] indicated the

relevance of the mixing method and the carbon nanotube treatment and its content

on the wear resistance of epoxy resin with MWCNTs, with 1.0 wt.% being the

optimal loading of MWCNTs to achieve the minimum specific wear rate. Cui et al.

[26] demonstrated that the addition of MWCNTs to epoxy is an efficient method to

improve the wear resistance and to lower the friction coefficient; they demonstrated

that a 0.5-wt.% amino-functionalized MWCNT composite achieves a reduction of

41.3 % on the wear rate compared to neat epoxy.

In this work, the influence of the addition of commercially amino-functionalized

MWCNTs on the in-plane and out-of-plane mechanical performance of epoxy was

assessed, as well as the friction coefficient and the wear resistance under dry sliding

conditions of the modified epoxy in epoxy twill weave carbon FRC manufactured

using resin transfer molding (RTM). The composite was designed with ca. 50 %

fiber volume fraction and the nFRC includes 0.3 wt.% of MWCNTs in the resin.

These values were set in agreement with the mechanical requirements (heavy-duty

machine elements conception) and the feasibility of achieving good MWCNTs

infiltration (see for example [27] and [28]) according to the selected manufacturing

procedure. The manufactured configurations were tested according to the ASTM D

3039 and ASTM D 4255 for the in-plane mechanical properties and according to

ASTM G 99 for the friction coefficient. Also, specific wear rate and through-

thickness compression test were performed according to [29]. The effects of the

MWCNTs on the composite were determined from the tests results.

Experimental description

Selected materials

The matrix is composed of the L20 epoxy resin with an EPH 161 hardener, which is

produced by Momentive, USA and purchased from R&G composites, Germany.

According to the technical data from the manufacturer, this resin system is designed

for heat resistant components up to 120 �C and groutings to approximately 10 mm

thick. In addition, curing occurs virtually free of shrinkage. The resin viscosity in

solution with the hardener at 25 �C is 700 cP and at 35 �C is 295 cP (the

measurements were made using a Fungilab Alpha series rotational viscometer). The

reinforcement is a twill 2/2 woven fabric of 204 g/m2 constructed by 200 tex

Carbon 3K yarns (the same in the warp and weft directions). The carbon fibers are

Tenax�—E HTA40 3K, and their manufacturer specifications are as follows: tensile

modulus of 238 GPa, tensile strength of 3950 MPa, density of 1.76 g/cm3 and ca.

1.3 % sizing based on epoxy resin. The fabrics are manufactured by Engineered

Polym. Bull.

123

Cramer Composites, Germany. Nanocyl (Belgium) provided the NC 3152 NH2

surface-modified MWCNTs. The MWCNTs are produced via the catalytic carbon

vapor deposition process.

Manufacturing process

The materials studied were manufactured using RTM. In this procedure, the resin is

injected into the mold at 4 bar and the composite is cured at room temperature for

24 h and post-cured for 15 h at 100 �C. The differences between the FRC and the

nano-engineered FRC (nFRC) were due to the resin preparation and the injection

temperature. For the FRC, the mixing ratio is 100:25 parts by weight of resin to

hardener mixed using mechanical stirring at room temperature. In the preparation of

the nFRC, 0.3-wt.% MWCNTs are poured into the resin and mixed in a propeller

stirrer (Velp, model Stirrer Type BS) for 10 min at 520 rpm. The mixture is then

placed in an ultrasonic bath (Elma, model Elmasonic P) at 30 �C for 90 min at

80 kHz. Because the addition of MWCNTs contributes to increase the resin

viscosity up to 840 cP, the mixture is then heated to 35 �C to obtain a viscosity

below 380 cP, followed by adding the hardener (at a 100:25 weight ratio) and

stirring the solution. The infusion is performed at 35 �C, and the mold is pre-heated

at the same temperature. A visual inspection of the doped epoxy on the inlet and

outlet hoses of the system is used to verify that MWCNTs filtration or precipitation

did not occur.

Two composites geometries were manufactured by means of the procedure above

described. The first one is a 12 plies laminate of 544 mm 9 250 mm 9 2.8 mm

used to characterize the in-plane mechanical behavior. The second one is a 45 plies

laminate of 250 mm 9 150 mm 9 10 mm used to obtained the specimens for the

through-thickness compression and tribological tests.

Laminates features

The laminate thickness is measured in at least ten points per manufactured laminate

using a Vernier caliper. The density is measured by immersion method according to

ASTM D 792 standard (five samples per material). The fiber volume fraction is

computed according to the ASTM D 3171 (method II). The hardness is measured

with a Barcol (Impressor GYZJ-934-1) as indicated the ASTM D 2583 and the

micro-Vickers hardness (using 500 g load during 10 s) is additionally measured for

the 45 plies laminates. All of this information is presented in Table 1, where the

same physical properties of the materials is achieved (Fiber volume fraction and

Density are similar).

Mechanical tests

The mechanical performance of the materials is determined from in-plane tensile

tests, in-plane shear tests and through-thickness compression tests. All the tests were

performed under quasi-static conditions in an Instron 8801 testing machine provided

with a 100 kN load cell. The specimens were cut by diamond wheel cutter. The

Polym. Bull.

123

mechanical parameters are presented in Table 2, where each value was obtained

from the average of five tests. In this table, the average value (AV) is complemented

with the standard deviation (SD), the relative standard variation (R. SD) and the

95 % interval of confidence (IC).

Tensile tests

The tensile tests were performed according to the ASTM D 3039 with a crosshead

speed of 1 mm/min. The specimens were obtained from the 12 plies laminates. The

specimens were clamped using hydraulic wedge grips. The stress was computed

from the load cell data and the initial specimen cross section. The longitudinal strain

was measured using a strain gage (length: 9.5 mm, width: 3.5 mm, gage length:

5 mm, gage factor 2.1, gage resistance: 120 X). The elastic modulus was computed

using a linear regression on the linear (elastic) range of the stress–strain curve and

the tensile strength was set at the maximal stress level.

In-plane shear tests

The in-plane shear tests were performed according to the ASTM D 4255 at a

crosshead speed of 0.3 mm/min. A two-rail testing device was embedded into the

testing machine. The specimens were obtained from the 12 plies laminates. The

Table 1 Laminates features

Number

of plies

Material Parameter Average

value

Standard

deviation (SD)

Relative

SD %

12 FRC Thickness (mm) 2.81 0.08 2.8

Density (g/cm3) 1.46 0.01 0.7

Fiber volume fraction 0.49 0.02 4.1

Barcol hardness 65.1 4.7 7.2

nFRC Thickness (mm) 2.77 0.09 3.2

Density (g/cm3) 1.45 0.01 0.7

Fiber volume fraction 0.51 0.02 3.9

Barcol hardness 66.7 4.4 6.6

45 FRC Thickness (mm) 10.18 0.04 0.4

Density (g/cm3) 1.43 0.01 0.7

Fiber volume fraction 0.52 0.01 1.9

Barcol hardness 61.7 3.6 5.8

Micro-Vickers hardness 38 14 37

nFRC Thickness (mm) 10.19 0.07 0.7

Density (g/cm3) 1.44 0.01 0.7

Fiber volume fraction 0.52 0.01 1.9

Barcol hardness 61.2 6.0 9.8

Micro-Vickers hardness 36 15 42

Quality control for both types of plates studied

Polym. Bull.

123

stress was computed from the load cell data and the initial specimen cross

section. The shear strain was measured using a strain gage (length: 9.5 mm, width:

3.5 mm, gage length: 5 mm, gage factor 2.1, gage resistance: 120 X) that was

placed as indicated in the norm. The in-plane shear modulus was obtained using a

linear approach for a shear strain range of 0–0.002 (due to the non-linear elastic–

plastic behavior of the material under the imposed condition) and the shear strength

was set at the achievement of a shear strain of 0.05, according to the norm.

Out-of-plane compression tests

The out-of-plane compression tests were performed according to [29] at a crosshead

speed of 0.5 mm/min. The specimens were 10 mm 9 10 mm 9 10 mm cubes

obtained from the 45 plies laminates. The specimens were compressed between two

lubricated steel plates. The stress was computed from the load cell data and the initial

specimen cross section. The longitudinal strain was measured using a strain gage

(length: 6 mm, width: 2.5 mm, gage length: 2 mm, gage factor 2.0, gage resistance:

120 X). The through-thickness compressive elastic modulus was computed using a

linear regression on the linear (elastic) range of the stress–strain curve and the

through-thickness compression strength was set at the maximal stress level.

Tribological testing

The tribological tests were performed on a pin on disk apparatus (High Temperature

Tribometer from CSM Instruments) under dry sliding conditions (Fig. 1). The

Table 2 Mechanical properties of material composites prepared

Test Parameter Material AV SD R. SD % Limits of

IC (95 %)

Tensile Elastic modulus (GPa) (TM) FRC 54.1 1.4 2.6 ±2.6

nFRC 55.9 1.7 3.0 ±3.1

Tensile strength (MPa) (TS) FRC 692 81 11.7 ±149

nFRC 692 47 6.8 ±86

Poisson ratio, m (PC) FRC 0.058 0.008 13.8 ±0.015

nFRC 0.058 0.014 24.1 ±0.026

Ultimate strain (US) FRC 0.012 0.001 8.3 ±0.002

nFRC 0.011 0.001 9.1 ±0.002

In-plane shear Shear modulus (GPa) (SM) FRC 3.3 0.6 18.2 ±1.1

nFRC 3.5 1.1 31.4 ±2.0

Shear strength (MPa) (SS) FRC 49 3.4 6.9 ±6.2

nFRC 49 5.3 10.8 ±9.7

Through-thickness

compression

Elastic modulus (GPa)

(TTCM)

FRC 8.7 0.8 9.2 ±1.5

nFRC 9.3 1.2 12.9 ±2.2

Compressive strength MPa

(TTCS)

FRC 637 20 3.1 ±37

nFRC 690 26 3.7 ±48

Polym. Bull.

123

specimen is a 38 mm 9 38 mm 9 10 mm 45 plies composite, which is fixed on the

machine. The specimen is perpendicularly loaded by a stainless steel ball that slides

(without rotation) over the material surface following a circular path (as shown in

Fig. 2). The imposed load (F) is set to 2 N, the ball diameter is 10 mm and its speed

(v) is set to 0.98 m/s. The testing equipment records the frictional force during the

test to compute the friction coefficient. The initial pressure (p) imposed by the ball

over the specimen is approximately 107.5 MPa for the nFRC and 102.7 MPa for the

FRC, as computed by the Hertz contact theory using the data from Table 2, leading

to the pv testing condition of 105.4 and 100.6 MPa m/s for the nFRC and the FRC,

respectively.

Fig. 1 Pin on disk apparatus. Tribological properties are studied in it

Fig. 2 Wear specimen. Wearpath over the specimen isobserved after test

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123

The tests were performed at three sliding distances (L): 10,000, 30,000 and

50,000 m. Each test was repeated three times (new specimens were used in every

test). The mass of each of the specimens was measured before and after performing

the tests using a balance (precision of 0.01 mg). The mass loss (Dm) was used in the

Eq. 1 to determine the specific wear rate (q denotes the density of the specimen

established on Table 1).

Wr ¼ DmqFL

mm3=N m� �

: ð1Þ

Results and discussion

Mechanical Properties

The obtained mechanical properties for FRC and nFRC composites from quasi-

static tensile, shear and compression tests are summarized in Table 2. The

normalized material parameters with respect to the values from the FRC composite

are shown in (Fig. 3) in order to facilitate the comparison of the mechanical features

under consideration.

It is assumed, as established in the introduction, that the inclusion of the

MWCNTs improves the strength of the matrix/reinforcement interface and the

matrix fracture toughness. Under quasi-static conditions, for tensile tests the effect

of the improved strength is negligible. Likewise, a similar result is presented in [30].

The same result was found for the in-plane shear test, at least under the studied

strain range, where the matrix behavior had a major role (see, for example, the

explanation presented in [31]). The increase of the nFRC through-thickness

compressive strength is attributed to the influence of the performance of the

improved matrix/reinforcement interface on the failure mechanisms (see [32, 33] for

a deeper study on the influence of the interface).

Fig. 3 Normalized material parameters. A comparison of mechanical properties is shown and it ispossible to see improvements in some properties due to carbon nanotubes addition

Polym. Bull.

123

Tribological tests

Figure 4 illustrates the steady-state friction coefficient during the test. It can be

observed that the friction coefficient is similar for every case. On the other hand,

Figs. 5 and 6 indicate the measured mass loss and specific wear rate (computed

using Eq. 1) for both material configurations at the different sliding distances. The

average values are used to develop the ideas established in the following paragraphs

(note that the results obtained from the nFRC are more stable). Figure 5 shows that

at 10,000 m of sliding distance, there is not a remarkable difference on the mass loss

between the FRC and the nFRC. However, at 30,000 and 50,000 m sliding

distances, the amount of mass loss is lower for the nFRC.

Fig. 4 Friction coefficient.Variation of coefficient duringthe tests in both materials areobserved, similar values areobserved in almost all cases

Fig. 5 Mass loss. Mass loss ofthe specimen for differentsliding distances shown thesame behavior but lower valuesfor nFRC

Fig. 6 Wear rate. Specific wearrate are observed for differentsliding distances and it ispossible to see a reduction forhigher distances in nFRC

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123

Figure 6 shows that the specific wear rate for the FRC is similar at the tested

sliding distances. Note that the specific wear rates for the nFRC experiences a

reduction of the specific wear rate at the higher sliding distances. The results

obtained from the tribological tests indicate that FRC and nFRC do not change the

value of the steady-state friction coefficient considerably. This result, together with

the fact that the behavior of both material configurations at a sliding distance of

10,000 m is similar in mass loss and specific wear rate (due to the high influence of

the surface resin layer), is used to deduce that the role of the transfer film at this

stage is not altered by the amount of MWCNTs contained in the nFRC debris. In

this case, the improvement on the wear resistance reported in [26] for epoxy resin

with a similar amount of amino-functionalized MWCNTs, but for different loading

conditions, were not reproduced. Nevertheless, reducing specific wear rate for nFRC

at higher sliding distances is associated with the CNTs influence on matrix/fiber

interface, helping to reduce interfacial debonding and keep the broken fiber in the

composite surface due to mechanical interlocking of CNTs with matrix, chemical

bonding between CNTs and bulk materials and local stiffening of polymer matrix

near fiber/matrix.

Microscopic analysis

The worn surfaces of the specimen at the different sliding distances were observed

using a scanning electron microscope (SEM, JSM-6380 JEOL). The worn surfaces

of the specimens were cleaned and then coated with a thin gold layer. Figures 7

and 8 show selected micrographs of the surfaces of FRC and nFRC, respectively.

The selection was based on the representativeness of the wear mechanisms. In

both figures, the images (a) and (b) represent the specimens state at a sliding

distance of 10,000 m, (c) and (d) at 30,000 m and (e) and (f) at 50,000 m. In the

figures, the blue arrow represents the sliding direction. Figure 7a shows the effects

when the pin passes over a poorly impregnated area, where it is possible to

identify: (1) the boundary between the original surface and the first ply of visible

fiber; (2) a transversally broken fiber; (3) the debris trapped between fibers; (4) an

obliquely broken fiber; (5) the beginning of fiber-matrix debonding. Figure 7b

shows the behavior of the material in a well-impregnated zone, where it is

possible to observe micro-plowing marks in the sliding direction and: (1) fractured

fiber; (2) fiber pullout and the subsequent disorientation of the removed material;

(3) the beginning of fiber-matrix debonding.

In Fig. 7c, d, micro-cracking was the most commonly observed phenomenon.

Figure 7c shows: (1) and (4) a micro-crack that divides the matrix; (2) and (3)

broken fibers; (4) several micro-cracks in the original surface. Figure 7d shows: (1)

fiber pullout; (2) broken fibers disoriented in the sliding direction; (3) and (4) micro-

cracking and the resin debonding zone. Figure 7e shows: (1) and (2) several broken

fibers; (3) the boundary between the worn surface and the resin surface parallel to

the sliding direction. Figure 7f presents: (1) and (2) plowing marks on the matrix

due to plastic deformation in the resin, which, according to [7], occurs through the

application of cyclic loads on the specimens and the generation of high temperatures

Polym. Bull.

123

(approaching Tg) in some points associated to the real contact area; (3) shows

debonding of the fiber-matrix zone.

Figure 8 shows a selection of the most common wear mechanisms observed

during the SEM inspection of the nFRC; note that these mechanisms are the same as

those in the former case. Nevertheless, the frequency of these wear mechanisms,

especially matrix cracks, were much lower for nFRC than for FRC. According to the

evidence, the improvement experienced by the nFRC on the wear resistance at

higher sliding distance is attributed to the influence of the MWCNTs content on the

Fig. 7 SEM images of FRC. a, b Represent sliding distance of 10,000 m where the first wearmechanisms are observed. c, d Corresponding to 30,000 m, micro-cracking and broken fiber are present.e, f Are images for 50,000 m, several wear mechanisms are observed

Polym. Bull.

123

increase of the IFSS and on the matrix fracture toughness and hence, according to

[10] to the improvement to the wear reduction.

The main idea was taken into account for the development of this work was to

use carbon nanotubes (MWCNTs) functionalized with amine groups. These groups

(–NH2) covalently anchored to the MWCNTs could operate in the same way as

operating the hardener used in this type of curing reaction (Previous antecedents

showed a shift of the amine signal belonging to the nanotubes after the curing

process). Therefore, when reacting the epoxy groups with the amino groups of the

hardener and nanotubes, it is likely to be formed a three-dimensional network where

the nanotubes are incorporated, as shown in Fig. 9. The resin components used were

Fig. 8 SEM images of nFRC. SEM images of nFRC. a, b Represent sliding distance of 10,000 m. c,d Corresponding to 30,000 m. e, f Are images for 50,000 m. The same wear mechanisms are present butin a much lower frequency

Polym. Bull.

123

bisPhenol-A-Epichlorhydrin (70 %), Bisphenol-F-Epichlorhydrin (20 %) and an

epoxidized molecule that gives flexibility to the thermoset polymer as 1.6-Bis(2.3-

Epoxypropoxy)hexane (10 %). On the other hand, the hardener is composed of

diethylenetriamine (50 %), Bisphenol A (49 %) present as a solvent and

m-phenylenebis(methylamine) (1 %). Basically, all the curing reaction focuses on

bisphenol A and F (Epichlorhydrin) and diethylenetriamine, coupled with the amine

groups of the MWCNTs.

Depending on the chemical structure of curing agent used and conditions of cure,

it is possible to obtain thermosetting polymers with mechanical properties ranging

from extreme flexibility to full hardness and rigidity, high adhesive strength, good

tensile properties and high temperature insulation. Therefore, a possible increase in

the degree of crosslinking because the (NH2)-MWCNTs, would mean an

improvement in the mechanical properties of the composites. However, this was

not found in the above results (this may be because the fiber can decrease the degree

of crosslinking of the resin). In Table 2, a significant improvement in the

compounds are not evidenced; this can be seen by comparing the obtained material

with and without (NH2)-MWCNTs. But, although the friction coefficient does not

change, the specific wear rate if tends to reduce. The above occurs because

functionalizing nanotubes create defects in both walls at its ends, in many cases the

tubes are broken into smaller pieces resulting in a drastic loss in mechanical and

electrical properties. The improvement in the rate of wear is due to the nanotubes

improve the matrix/reinforcement interface. But due to its functionalization it is not

sufficient to reduce the coefficient of friction of the material because their

mechanical properties decreased.

Fig. 9 Mechanism of the curing reaction using (NH2)-MWCNT and different types of crosslinkers. Athree-dimensional covalent network coupled with the nanotubes is obtained

Polym. Bull.

123

Conclusions

From the dry-sliding tribology tests (pin on disk) the inclusion of MWCNTs on the

composite were found to (a) not modify the friction coefficient and (b) tend to

reduce the specific wear rate. It can be remarked from the SEM images that the

nFRC exhibited a reduced amount of wear compared to the FRC, primarily in the

matrix cracking. This improvement of the wear resistance is attributed to the effect

of the MWCNTs on the enhancement of the strength of the matrix/reinforcement

interface and on the matrix fracture toughness and not to an improvement of the

resin transfers film effect.

The inclusion of the MWCNTs in the epoxy carbon FRCs manufactured by RTM

improves the through-thickness compressive stiffness and strength. Moreover, the

other mechanical properties under study are not affected by incorporating

MWCNTs.

Acknowledgments The financial support by CONICYT through the projects Fondef (D08i1138 and

IT13i10054) and CONICYT Regional (CIPA/R08C1002). The authors would like to thank the National

Commission for Scientific and Technological Research, CONICYT (Ministry of Education Government

of Chile) by PhD scholarship Grant No. 21100601 of G. Pincheira. The content is solely the responsibility

of the authors and does not necessarily represent the official views of the CONICYT.

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